Chemical Engineering and Industrial Chemistry

Predicting Solvation Thermodynamics in Water and Ionic Liquids using the Multi-Scale Solvation Layer Interface Condition (SLIC)

Authors

Abstract

We highlight the most recent developments of the solvation-layer interface condition (SLIC) continuum dielectric model in predicting solvation thermodynamics of neutral small molecules in water and multiple ionic liquids. We demonstrate that a simple temperature-dependent solvent-accessible-surface-area (SASA) correlation and a cavity-dispersion-combinatorial (CDC) theory, combined with the SLIC electrostatics model, provide highly accurate predictions of Gibbs solvation energies, solvation entropies, and solvation heat capacities. The SLIC/SASA model parameters are temperature dependent, whereas the SLIC/CDC parameters are constant. To address the lack of experimental data pertaining to the accuracy of the models, we conducted an extensive literature search and data compilation to obtain credible experimental solvation data. This yielded 159 and 123 data points for hydration entropies and heat capacities of neutral small molecules, respectively. Compared to experimental data, the SLIC/SASA and SLIC/CDC models, respectively, achieve an RMS error 1.39 (1.24) and 1.15 (1.76) kcal/mol for hydration free energy (hydration entropy) predictions. Solvation heat capacities are predicted with RMS errors 24.42 and 46.17 cal/mol/K. Most remarkably, the SLIC/CDC predictions of solvation entropies and heat capacities are made without apriori knowledge of experimental solvation entropies. In addition, the SLIC/SASA predictions of Gibbs solvation energies (solvation entropies) of 12 amino acid side-chain analogs in seven (three) ionic liquids are compared to the available explicit-solvent simulation data from Paluch et al.~\cite{Paluch12} and Latif~\cite{Latif14} et al.

Content

Thumbnail image of SLICpaper20210914.pdf